Surfactant processes

Abstract

A process for the preparation of surfactants is described comprising reacting a phosphorus acid ester of the following Formula (IV) ##STR1## wherein R t is aryl, R 2 is alkyl or aryl, with a hydrophilic polyoxyalkylene of the following Formulas (VIII), or (IX) ##STR2## wherein R 3 is alkyl and A is a hydrophilic polyoxyalkylene chain, and which reaction results in an intermediate compound Formulas (XI), (XII), or (XIII); ##STR3## reacting the intermediate compound selected from the group consisting of Formulas (XI) through (XIII), with a hydroxylic compound R 1 -OH (X) to yield surfactant precursors comprised of Formulas (V), (VI), and (VII), respectively: ##STR4## and, oxidizing said phosphorus ester-linked surfactant precursors selected from the group consisting of Formulas (V), (VI) and (VII), with an oxidizing agent to produce the surfactants.

What is Claimed is: 
     
       1. A process for the preparation of a compound represented by Formulas (I), (II) or (III); or optionally mixtures thereof ##STR27## wherein R 1  is a hydrophobic moiety of alkyl or aryl; R 2  is selected from the group consisting of alkyl and aryl; R 3  is hydrogen or alkyl; A is a hydrophilic polymer chain; and m is the number of repeating segments of the hydrophilic polymer chain A; and which process comprises: (a) reacting a phosphorus acid ester of the following Formula (IV) ##STR28## wherein R t  is aryl, R 2  is alkyl or aryl with a hydrophilic polyoxyalkylene of the following Formulas (VIII), or (IX) ##STR29## wherein R 3  is alkyl with from about 1 to about 6 carbon atoms, and A is a hydrophilic polyoxyalkylene chain, and which reaction results in an intermediate compound Formulas (XI), (XII), or (XIII), wherein component (XI) results from the reaction of phosphorus ester (IV) with polyoxyalkylene (VIII); component (XII) results from the reaction of phosphorus ester (IV) with polyoxyalkylene (VIII), and component (XIII) results from the reaction of phosphorus ester component (IV) with polyoxyalkylene glycol (IX) ##STR30## (b) reacting the intermediate compound selected from the group consisting of Formulas (XI) through (XIII), with a hydroxylic compound, R 1  -OH (X), to yield surfactant precursors comprised of Formulas (V), (VI), and (VII) respectively, wherein component (V) results from the reaction of component (XI) with R 1  -OH (X); component (VI) results from the reaction of component (XII) with R 1  -OH (X), and component (VII) results from the reaction of component (XIII) with R 1  -OH (X) ##STR31## wherein for (b) R t  is aryl, R 1  is alkyl or aryl, R 2  is alkyl or aryl, R 3  is hydrogen or alkyl, A is a hydrophilic polymer chain, and m is the number of repeating segments   (c) oxidizing said phosphorus ester-linked surfactant precursors (B) selected from the group consisting of Formulas (V), (VI) and (VII), with an oxidizing agent to produce the surfactant composition of Formulas (I), (II) or (III), wherein the surfactant (I) results from the oxidation of component (V), surfactant (II) results from the oxidation of component (VI), and surfactant (III) results from the oxidation of component (VII).   
     
     
       2. A process in accordance with claim 1 wherein there is accomplished a transesterification reaction of (a) and (b), and which reaction is effected by heating at a temperature of about 150° C. to about 250° C. under a reduced pressure of from about 1.0 to about 100 bar, and wherein the byproduct of R t  OH is optionally removed. 
     
     
       3. A process in accordance with claim 1 wherein the reactants for the formation of surfactant of Formula (I) comprise from 1 to about 1.2 molar equivalents of a phosphorus ester (IV), about 1.0 molar equivalent of a polyoxyalkylene (VIII), and from about 1.0 to about 1.2 molar equivalents of (X). 
     
     
       4. A process in accordance with claim 1 wherein the reactants for the formation of Formula (II) comprise from 1 to about 1.2 molar equivalent of a phosphorus ester (IV), and about 2.0 molar equivalents of a polyoxyalkylene (VIII). 
     
     
       5. A process in accordance with claim 1 wherein the reactants for the formation of Formula (III) comprise from 2 to about 2.4 molar equivalents of a phosphorus ester (IV), about 1.0 molar equivalent of a polyoxyalkylene (VIII), and from about 2.0 to about 2.4 molar equivalents of an alcoholic compound (X). 
     
     
       6. A process in accordance with claim 1 wherein there is accomplished a transesterification reaction of (a) and (b), and which reaction further includes a catalyst, and which catalyst is selected from the group consisting of metal salts, alkaline metal hydroxides, and alkaline metal alkoxides. 
     
     
       7. A process in accordance with claim 6 wherein said metal catalyst is magnesium chloride. 
     
     
       8. A process in accordance with claim 1 wherein the oxidation (c) is accomplished in an inert solvent at from 0° C. to about 60° C. with an oxidizing agent selected from the group consisting of hydrogen peroxide, ozone, organic hydrogen peroxides, and peracids. 
     
     
       9. A process in accordance with claim 8 wherein said oxidizing agent is hydrogen peroxide or tert-butyl hydrogen peroxide. 
     
     
       10. A process in accordance with claim 8 wherein said inert solvent is ethyl acetate, toluene, or dichloromethane. 
     
     
       11. A process in accordance with claim 1 wherein said R t  of the phosphorus ester of Formula (IV) is selected from the group consisting of phenyl, tolyl, fluorophenyl, and chlorophenyl. 
     
     
       12. A process in accordance with claim 1 wherein R t  is a phenyl. 
     
     
       13. A process in accordance with claim 1 wherein R 1  alkyl contains from about 4 to about 60 carbon atoms, R 1  aryl contains from about 6 to about 60 carbon atoms; R 2  alkyl contains from about 1 to about 60 carbon atoms, R 2  aryl contains from about 6 to about 60 carbon atoms; R 3  alkyl contains from 1 to about 6 carbon atoms; and m is a number of from about 2 to about 500. 
     
     
       14. A process in accordance with claim 1 wherein A is a hydrophilic polyoxyalkylene chain derived from the same or different alkylene oxides with from about 2 to about 4 carbon atoms. 
     
     
       15. A process in accordance with claim 1 wherein R 1  is an alkylaryl, and wherein alkyl contains from about 4 to about 30 carbon atoms and aryl contains from about 6 to about 10 carbon atoms; R 2  is an alkyl containing from 1 to about 30 carbon atoms or an aryl containing from about 6 to about 10 carbon atoms; R 3  is hydrogen or alkyl of from 1 to about 3 carbon atoms; and wherein A is a hydrophilic polyoxyalkylene chain with the number of repeating segments m being from about 5 to about 100. 
     
     
       16. A process in accordance with claim 1 wherein A is a poly(ethylene glycol) chain with the number of repeating units m being from about 5 to about 100. 
     
     
       17. A process in accordance with claim 1 wherein R 1  is an alkylphenyl group wherein alkyl contains from about 4 to about 30 carbon atoms, R 2  is a phenyl, and R 3  is a methyl, and wherein A is a poly(ethylene glycol) chain with the number of repeating units m being from about 5 to about 100. 
     
     
       18. A process in accordance with claim 1 wherein said compound resulting is selected from the group consisting of poly(ethylene glycol)-α-methyl ether-ω-p-tert-octyldiphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ω-octyldiphenyl phosphate, poly(ethylene glycol)-αmethyl ether-ω-decyldiphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ω-dodecyldiphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ωhexadecyldiphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ωmethyl p-tert-octylphenyl phosphate, bis -ω-p-tert-octylphenyl phosphate, poly(ethylene glycol)-α,ω-methyl p-tert-octylphenyl phosphate, poly(ethylene glycol) ethyl p-tert-octylphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ω-ethyl p-tert-octylphenyl phosphate, poly(ethylene glycol)-α-methyl ether-ω-p-tert-octylphenyl tolyl phosphate, poly(ethylene oxide-co-propylene oxide)-α-methyl ether-ω-p-tert octyldiphenyl phosphate, and wherein the polymer chain contains from about 5 to about 50 repeating units or segments. 
     
     
       19. A process in accordance with claim 1 wherein R t  is phenyl, R 1  is 4-octylphenyl or 4-dodecylphenyl, R 2  is a phenyl or methyl, and R 3  is a methyl. 
     
     
       20. A process in accordance with claim 1 wherein the hydrophobic compound R 1  -OH (X) is 4-tert-octylphenol or 4-dodecylphenol. 
     
     
       21. A process in accordance with claim 1 wherein said phosphorus ester is triphenyl phosphite. 
     
     
       22. A process in accordance with claim 1 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, ozone, organic hydrogen peroxides and peracids. 
     
     
       23. A process in accordance with claim 1 wherein the oxidizing agent is selected from the group consisting of tert-butyl hydrogen peroxide, cumene peroxide, peracetic acid and performic acid. 
     
     
       24. A process for the preparation of a poly(ethylene glycol)-α-methyl ether-ω-p-tert-octyldiphenyl phosphate comprising the reaction of about 1.0 molar equivalent of poly(ethylene glycol) monomethyl ether with M n , of from about 500 to about 2,000, from about 1.0 to about 1.5 molar equivalents of triphenyl phosphite, from about 1.0 to about 1.5 molar equivalents of 4-tert-octylphenol, and from about 0.01 to about 0.05 molar equivalent of magnesium chloride, with an oxidizing agent and wherein the oxidation optionally includes from about 1.0 to about 1.5 molar equivalents of hydrogen peroxide. 
     
     
       25. A process for the preparation of a component represented by Formulas (I), (II) or (III); or optionally mixtures thereof ##STR32## wherein R 1  is a hydrophobic moiety; R 2  is a suitable aliphatic or aromatic group; R 3  is hydrogen or aliphatic; A is a hydrophilic polymer chain; and m is the number of repeating segments of the hydrophilic polymer chain A; and which process comprises (a) reacting a phosphorus acid ester of the following Formula (IV) ##STR33## wherein R t  is aryl, R 2  is a suitable aliphatic or aromatic group with a hydrophilic polyoxyalkylene of the following Formulas (VIII), or (IX) ##STR34## wherein R 3  is alkyl, and A is a hydrophilic polyoxyalkylene chain, and which reaction results in a compound of Formulas (XI), (XII), or (XIII), wherein component (XI) results from the reaction of phosphorus ester (IV) with polyoxyalkylene (VIII); component (XII) results from the reaction of phosphorus ester (IV) with polyoxyalkylene (VIII), and component (XIII) results from the reactions of phosphorus ester component (IV) with polyoxyalkylene glycol (IX) ##STR35## (b) reacting the compound selected from the group consisting of Formulas (XI) through (XIII) with a hydroxylic compound R 1  -OH (X) to yield compounds of Formulas (V), (VI), and (VII), respectively, wherein component (V) results from the reaction of component (XI) with R 1  -OH (X); component (VI) results from the reaction of component (XII) with R 1  -OH (X), and component (VII) results from the reaction of component (XIII) of R 1  -OH (X) ##STR36## (c) oxidizing said phosphorus ester-linked compound (b) selected from the group consisting of Formulas (V), (VI) and (VII), with an oxidizing agent to generate Formulas (I), (II) or (III), wherein (I) results primarily from the oxidation of component (V), (II) results primarily from the oxidation of component (VI), and (III) results primarily from the oxidation of component (VII).